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Although nanostructure engineering and hybridization with conductive materials have been proposed to address this concern, a better performance toward practical device applications is still highly desired. Herein, we report an iron-doping-induced structural phase transition from pyrite-type (cubic) to marcasite-type (orthorhombic) phases in porous carbon/rGO-coupled CoSe2. The dual-carbon-confined orthorhombic CoSe2 (o-FexCo1-xSe2@NC@rGO) composites exhibit dramatically enhanced lithium storage performance (920 mAh g(-1) after 1000 cycles at 1.0 A g(-1)) over cubic CoSe2-based composites (c-CoSe2@NC@rGO). The combined experimental studies and density functional theory calculations reveal that this doping-induced structural phase transformation strategy could create a favorable electronic structure and ensure a rapid charge transfer. 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